JPS6075677A - Yarn sizing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for sizing continuous filament yarns using a resin system. The present invention relates in particular to a method for sizing continuous filaments used in reinforced plastics with a resin system that is the same as or compatible with the plastic being reinforced.

[Conventional technology]

Fibers used in the manufacture of reinforced plastics may be pre-coated with resin before being used as reinforcement. Coating with such resins is typically accomplished by first applying a variety of methods to the fibers, such as solution coating, melt coating with a curing composition, and then partially curing the coated fiber composite. .

The usual purpose of preliminary partial curing is to obtain relatively dry handling conditions and to obtain flexible fibers. Mats or sheets that are woven or have randomly arranged fibers are typically made from coated fibers. The mat or sheet is later molded by itself or with the addition of resin, during which time the main curing is carried out and the final
It is disclosed in No. 5. There, a dry roll of continuous fibers or filaments is placed in a container.
The roll is degassed to remove any air trapped within it, and then the roll is immersed in a liquid containing an initially non-crosslinking thermosetting agent. The pressure is continued until the resin medium of the resin catalyst and solvent substantially fills the voids in the roll.

This patent teaches lifting the roll from any remaining unabsorbed resin media and heating to partially cure the resin. It is also taught that heating removes all or most of the solvent present in the original resin medium. This method also teaches that there is no need to unwind the fibers from the rolls to prevent them from soaking up the resin.

This patent further teaches that the treatment of rolled glass fibers is carried out with an epoxy resin solution in, for example, acetone, containing a catalyst for the epoxy, i.e., a curing agent, such as an amine.

The solvent is 10 to 300% relative to the resin and curing agent.
It is also taught that amounts in weight percent are required.

[Problem that the invention seeks to solve]

However, if a drying roll with a continuous glass filament is immersed in an acetone solution of an epoxy resin containing an amine curing agent according to this teaching, then the epoxy coating on the glass filament is dried and cured;
Even when the rolls are cooled, the isolated exothermic reaction within the rolls causes uncontrolled curing, and the resulting coated and overcured glass filaments are difficult to further process for the production of reinforced plastics. It was discovered that

Therefore, there is a need for a) method that can provide epoxy-coated fiber composites under controlled conditions.

Additionally, there is a need in many composite plastics applications for a method of making filaments coated with very small amounts of partially cured epoxy resin to strengthen the filaments. Here, we will refer to this as ``filament sizing,'' which involves applying a ``sizing amount'' of partially cured epoxy resin onto the filament.The overall purpose of this method is to The goal is to supply yarn in its original state.

[Failure to solve the problem]

The filament sizing method according to the present invention includes the following steps.

A, less than saturated amount of unsaturated epoxy resin and crosslinking and curing with it; 1? A solution of a ketone solvent containing a polyamine and chemically interfering with the crosslinking of the polyamine with the epoxy resin is added to a container with a vapor space above the solution, and is rolled up into the solution. B. Immersing the filament in the solution under substantially atmospheric pressure until the solution is substantially immersed in the solution; C. Into the vapor space. D. removing the vacuum and removing the roll from the solution and placing the roll in a suitable container. E. Degassing the appropriate container to remove residual ketone solvent from the roll, thereby unblocking the polyamine curing agent and removing the B of the epoxy by the curing agent onto the filament. A step of partially crosslinking to stage hardening; The xy resin is about 0.5% to about 15% by weight of the filament.
G. removing the roll of sized filament coated on the filament;
This is a step of cooling to 0°C or lower, preferably 0°C or lower, to stop the crosslinking reaction.

In carrying out the invention, the yarn is comprised of a large number of filaments. Such filaments may be lightly roving or roped filaments. Alternatively, filaments formed on a fabric may be used.

The roll is first immersed in the ketone solution, usually under normal conditions, i.e. at a temperature of 20° to 30°C and a pressure of atmospheric pressure, and air bubbles from the immersed roll stop rising to the surface of the solution. soaked until The time period is approximately 0.5 to 2 hours, but may be more or less than this.

The vessel is closed and vacuum is applied above the solution until additional air bubbles stop rising into the vapor space. This operation is usually performed at room temperature. Degassing is from about 1001m to about 600m in mercury column.
m, but may be higher or lower depending on the required residual air removal rate. The exact time when the air bubbles stop rising is not always easily determined. This is because inspection of the surface of a solvent in a closed container must be carried out intermittently unless the container itself is made transparent.Therefore, sufficient time is allowed.

Alternatively, if desired, an initial soaking step of (B) and (C)
The pressure may be reduced immediately after the roll is immersed in the solution.

In the present invention, the actual depressurization is not considered critical, and the vacuum ranges described are based on 7 GO mm of mercury as a total or absolute vacuum.

The purpose of removing air under reduced pressure is to remove any residual air contained or trapped within the roll, thereby allowing the roll of filament to more thoroughly penetrate.

The vacuum is released and the roll is removed from the solvent and preferably placed in another container instead of draining the solution from the first container to prevent contamination by a film forming on the walls of the first container. .

The ketone solvent is also removed from the roll in the second container;
Degassing is performed to prevent curing by the amine.

This is the most important part of this process and is described in US Patent No. 3.
This is an essential difference from the conventional process disclosed in No. 384.505. In the present invention, crosslinking is more effectively controlled in the state of the sizing yarn wound up on a roll, and the sizing yarn is manufactured.

When carrying out the process of the conventional method, since air cannot be effectively removed from the roll, an uncontrolled crosslinking reaction can easily proceed within the roll, thereby causing a large exothermic reaction throughout the roll, which makes it difficult to carry out the present invention. It was observed that a relatively thick and wide coating was applied to the filament compared to the more minimal sizing amount of resin obtained by the method. Additionally, it has been observed that crosslinking of the resin is difficult to control.

In fact, according to the process of the present invention, a more controlled crosslinking of the resin coating is achieved because the rate of crosslinking is proportional to the rate at which the ketone solvent is removed from the saturated roll under degassing. Furthermore, the rate of exothermic reactions can be reduced, thereby reducing the heat generated by the entire roll.

The degree of B-stage cure is related to the degree of partial crosslinking of the epoxy coating so that the filaments have a dry feel and are therefore easier to handle in subsequent molding and other steps.

Additionally, the epoxy resin can later be cured or crosslinked beyond the B-stage cure into a thermoset polymer. B
Stone F+ in staged hardening? The viscosity of oxidizer is typically 2
About 9.000 to about 1 s, o o (1 poise) at 5°C.

The B-stage cured coating is cooled after the partial crosslinking step, and the cooling is typically kept below at least 5° C. and stored until it is used.

The processing time for sizing in a vacuum vessel for solvent removal is approximately 25 minutes with optionally warmed air or inert gas.
It can be reduced by alternately or periodically blowing into the container at a temperature on the order of 50°C to about 50°C.

It is important that the solution not be saturated with both the epoxy resin and the polyamine.

This is because sediments and precipitates of resins and curing agents can quickly release the blocking reaction of ketones and make it difficult to control the intense exothermic reaction in the wound filament, which leads to defective sized filaments. is easily molded.

The sized yarn according to the present invention can be used in filament winding, sheet molding composites, blow-up (5 prayu
p) Can be further processed for use in IIC-related pre-aligned fiber manufacturing techniques.

In the practice of the present invention, the amount of polyamine can be adjusted to Approximately 20 I) I) h to approximately 35 pp
An amount in the range of h (pph is 10
(means parts by weight relative to 0 parts by weight).

A typical solution contains from about 5 to about 20 ξ-cents by weight of epoxy resin and from about 2 to about 6 ξ-cents by weight polyamine.

Preferred solution concentrations are controlled by measurements using a liquid hydrometer. Usually the specific gravity at 25℃ is about 0.84 to 0.
．． 8'5 is preferable from the viewpoint of both preventing the formation of a saturated solution and controlling the amount of resin impregnated into the yarn.

Various fibrous materials can be used for the filaments in the practice of the present invention, such as glass, caryne, polyester, nylon, or aramid, or combinations of these filaments.

The unsaturated epoxy resin is typically a liquid epoxy resin, preferably having a molecular weight in the range of about 300 to about 600;
Viscosity is about 3,000 to about 35,000 at 25°C
Centipoise range and epoxide number from about 160 to about 5. OO.

Preferably it is about 170 to about 190.

Representative examples of such epoxy resins include diglycidyl ether of hisphenol A, epoxy nodelac resin, and aliphatic cyclic epoxy P. Here, the aliphatic cyclic group is epoxidized with an olefinic group and has a total number of carbon atoms ranging from about 7 to about 26. Most preferred are diglycidyl ethers to bisphenols.

In the present invention, the polyamine is selected from primary or secondary aromatic or aliphatic polyamines. Diamines are usually preferred.

A typical example of an aromatic amine is methylene dianiline (
MDA), metaphenylenediamine (MPDA), diaminodiphenylsulfone (DAD, S), m-xylylenediamine, orthophenylenediamine and diethyl-24-tonolenediamine. MDA and MPDA are preferred.

Representative examples of aliphatic diamines include diethylenetriamine (DETA), triethylenetetramine (TE'I'
A), Tetraethylene phosphorus amine (TEPA), Cyphethyl-aminopropylamine, Monoethanolamine,
These include aminoethylpiperazine, amineethylethanolamine, and 1,2-diaminocyclohexane. D
ETA and TETA are preferred.

Representative examples of liquid ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), diethyl ketone, tertiary-butyl methyl ketone, 2-hexanone, hexanone, and cyclohexanone.

The method of the invention is further illustrated by the following example. The sillage is within the scope of the present invention, and the centage is based on weight.

[Example] About 1.600 to about 2. The diameter of the roll is about 30.5 cm, the width is about 33 CrrL, and the inner diameter is about 15 (m
(This is in the form of a roll of PPG Industries Kanno ξ knee to Hy-i 7 (Hy
bon) 2078-67s). The term roving refers to untwisted filament threads. The filaments within the yarn are therefore essentially parallel to each other. The yarn is a continuous thread with a weight of 735 grams per kilometer and a width of about 25 mm.
Each filament has a diameter of about 96 to about 248 microns.

The roll of filament is weighed and placed into a container;
The composition of the acetone solution is 100 parts acetone, 3.98 parts methylene dianilin, 13.26 parts by weight Dow Chemical Co., known as DER 332. The acetone solution consists of an epoxy resin of the diglycyl ether of bisphenol A with a molecular weight of about 300 and an epoxy value of about 174.The acetone solution has a concentration below saturation, so no precipitation of diamine or epoxy should be observed. The specific gravity of this solution is about 0844 as measured with a hydrometer at about 23°C.

The acetone solution is prepared by weighing the ingredients and mixed in a dipping vessel.

A vapor space is formed in the acetone solution containing the immersion roll.

The dip roll is allowed to remain immersed in the acetone solution for about 15 minutes until air bubbles stop rising to the surface of the solution.

Degassing (pressure drop) is applied to the vapor space above the solution for approximately 1 hour to approximately 660 m1 of mercury (with 760 mm as reference to absolute vacuum) to remove any residual air in the immersion roll and further infiltrate the roll. to encourage

The roll is then pulled out of the solution, drained, placed in a second container, and degassed (pressure drop).
It takes 24 hours at about 6607 nR mercury and continues until the smell of acetone disappears. The ambient temperature during this step is approximately 23°C.

When residual acetone is removed from the roll by evaporation under degassed conditions, the diamine is chemically unblocked and in this state is partially crosslinked with the epoxy in the "B" stage on the filament.

The roll was then reweighed to determine the amount of resin sizing of the rolled up roving yarn, and the results were as follows.

Weight of roll before dipping 23,898 grams Weight of roll after solvent removal and B++ stage epoxy crosslinking 2
4,712 grams Weight of coated resin 814 grams Weight of coated resin/weight of filament 341% Prior to making a composite ring by compression molding, the skeleton was formed by the following steps.

A continuous thread of sized filaments of enhanced intact thread is chopped by an automatic machine to lengths of about 1 inch to about 8 inches (25 crfL to 20 CIrL). The cutting is then carried out according to the machine's program.

The chopped and sized yarn is oriented and pressed into a molded article (precursor) by a machine. The precursor thus formed is sprayed with a mixture of glycidyl ether-bisphenol A type epoxy resin containing a diamine crosslinker.

The resulting composite is then compression molded at about 160"C for about 1/4 hour to crosslink the sizing threads precured in the previous II B I+ step with the sprayed epoxy and stiffened. It is molded as a fiber-reinforced, heat-set epoxy product.

In order to illustrate the invention, representative embodiments and
Although details have been shown, it will be apparent to those skilled in the art that various modifications may be made without departing from the scope of the invention.

patent applicant THE GUTSU P EAR-TIRES AND Ranoguni Konnoguni agent Tadashi Wakabayashi

Claims (1)

[Claims] 1. Each of the following steps: A. Containing an unsaturated epoxy resin and a polyamine cross-linked and cured with the unsaturated epoxy resin in an amount less than the saturation amount, and chemically preventing the polyamine from cross-linking with the epoxy resin. B. Adding a solution of a ketone solvent into a container with a vapor space above the solution, and immersing a continuous thread of filament wound into a roll into the solution; immersing the roll in the solution at atmospheric pressure until it is substantially immersed in the solution; degassing the vapor space to remove residual air; D. Release the vacuum, remove the roll from the solution, and place the roll in a suitable container; E. Degas the suitable container. removing residual ketone solvent from the roll, thereby unblocking the polyamine curing agent and partially crosslinking the epoxy to a B-stage cure with the curing agent on the filament;
F, the weight percent of the filament with partially crosslinked epoxy υ released from the degassed state is about 0.5% to about 15%.
G. taking out a roll of sized yarn coated on the filament;
A filament sizing method comprising the steps of cooling to below ℃ to stop the crosslinking reaction. 2. d. The method according to claim 1, wherein the yarn is a multifilament roving or a filament rope-like undulating yarn. 3. The method according to claim 1, wherein the filament is one or more fibers selected from glass, carbon, polyester, nylon, and aramid. 4 The unsaturated epoxy resin has a molecular weight in the range of about 300 to about 600, and a viscosity of about 30 at 25°C.
00 to about 3.5000 centipoise and has an epoxy value in the range of about 160 to about 190, said polyamine being selected from primary or secondary aromatic or aliphatic diamines; 4. Process according to claim 3, characterized in that the ketone is selected from at least one of acetone, methyl ethyl ketone and methyl isobutyl ketone. 5. The epoxy is selected from at least one of diglycidyl ether of bisphenol A, epoxy nose rank resin, and aliphatic cycloevogicide whose alicyclic group is an olefin group with epoxy F, and the polyamine is Methylene dianiline, metaphenylene diamine, diaminodiphenylsulfone, l1l-xylylene diamine, orthophenylene diamine, noethyl-2,4-
) selected from at least one of luenediamine, dianilinetriamine, tetraethylenepentamine, diethylaminepropylamine, aminoethylpiperazine, aminoethylethanolamine and 1,2-diaminocyclohexane, and the ketone is acetone, methylethylketone, terX1l-butylethylketone, 2-
4. A method according to claim 3, characterized in that it is selected from at least one of hexane, 3-hexane and cyclohexanone. 6 The epoxy is a diglycidyl ether of bisphenol A having a molecular weight in the range of about 300 to about 600 and an epoxy P value in the range of about 170 to about 190, and the polyamine is methylene dianiline, metaphenylene diamine, noethylene triamine. and tetraethylenepentamine, and the tritone is selected from at least one of acetone, methyl ethyl ketone, and methyl isobutyl ketone. Method described. 7. The ketone solution has a specific gravity in the range of about 0.84 to about 0.85 at 25° C., and the sized filament is coated with the partially crosslinked epoxy coating in an amount in terms of weight percent of the filament. 6. The method of claim 5, wherein the amount is about 1% to about 10%. 8. The method according to claim 1 or 6, in which the above steps (B) and (C) are combined.